CN114551908B - Preparation method of gas diffusion layer with anti-counter electrode capability - Google Patents

Preparation method of gas diffusion layer with anti-counter electrode capability Download PDF

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CN114551908B
CN114551908B CN202210083876.1A CN202210083876A CN114551908B CN 114551908 B CN114551908 B CN 114551908B CN 202210083876 A CN202210083876 A CN 202210083876A CN 114551908 B CN114551908 B CN 114551908B
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graphene oxide
gas diffusion
diffusion layer
mixing
solvent
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CN114551908A (en
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高佳武
唐雪君
韩凯凯
赵航
张泽
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Dongfeng Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The present application relates to the field of fuel cells, and in particular, to a method for preparing a gas diffusion layer with anti-counter electrode capability; the method comprises the following steps: respectively obtain graphene oxide and Ni 3 S 2 Solids, dispersants, and crosslinkers; adding the graphene oxide into a solvent for mixing, and then adding the Ni 3 S 2 Mixing the solids to obtain a water electrolysis catalyst; mixing the water electrolysis catalyst, the dispersing agent and the cross-linking agent, and dispersing to obtain microporous layer slurry with anti-counter electrode capability; spraying the microporous layer slurry on a commercial gas diffusion layer to obtain a gas diffusion layer with anti-reflection capability; by adding Ni as a catalyst capable of improving the activity of hydrolysis reaction 3 S 2 The catalyst-supported graphene oxide is loaded on the graphene oxide, and the uniform distribution of the catalyst-supported graphene oxide can be ensured through the use of the dispersing agent and the cross-linking agent, so that the microporous layer slurry with anti-counter electrode capability is obtained, and then the microporous layer slurry is sprayed on the gas diffusion layer, so that the anti-counter electrode capability of the gas diffusion layer can be improved.

Description

Preparation method of gas diffusion layer with anti-counter electrode capability
Technical Field
The present disclosure relates to the field of fuel cells, and more particularly, to a method for preparing a gas diffusion layer with anti-counter electrode capability.
Background
The proton exchange membrane fuel cell is a power generation device for converting hydrogen energy into electric energy, has the advantages of high energy density and no emission pollution, and can obviously reduce the emission of carbon when being applied to the field of automobiles, so as to achieve the targets of carbon peak reaching and carbon neutralization; however, when proton exchange membrane fuel cells are used in the automotive field, it is most important to improve the performance such as power density and durability, and also to improve the anti-polarity capability.
The traditional method for improving the anti-counter electrode capability of the fuel cell is to add materials such as yttrium oxide into the catalyst, and the addition of the yttrium oxide material can delay the corrosion of carbon in the catalyst, so that the anti-counter electrode effect is achieved; however, according to the prior research results, the addition of the materials into the catalyst increases the ohmic internal resistance of the battery, and the electrochemical polarization of the materials increases, so that the catalytic performance of the catalyst is reduced.
However, in the anti-counter electrode test, the counter electrode phenomenon occurs not only at the catalyst level, but also on the microporous layer of the carbon paper, namely, the phenomenon that the carbon material is decomposed, thereby causing the hydrophobicity of the gas diffusion layer to be reduced, and further causing the performance of the fuel cell to be reduced; therefore, how to prevent the carbon material of the gas diffusion layer from being decomposed while ensuring the catalytic performance of the catalyst is a technical problem that needs to be solved at present.
Disclosure of Invention
The application provides a preparation method of a gas diffusion layer with anti-polarity reversing capability, which aims to solve the technical problem that a carbon material of the gas diffusion layer is easy to decompose under the condition of ensuring the catalytic performance of a catalyst in the prior art.
In a first aspect, the present application provides a method for preparing a gas diffusion layer with anti-counter electrode capability, the method comprising:
respectively obtain graphene oxide and Ni 3 S 2 Solids, dispersants, and crosslinkers;
adding the graphene oxide into a solvent for mixing, and then adding the Ni 3 S 2 Mixing the solids to obtain a water electrolysis catalyst;
mixing the water electrolysis catalyst, the dispersing agent and the cross-linking agent, and dispersing to obtain microporous layer slurry with anti-counter electrode capability;
and spraying the microporous layer slurry on a commercial gas diffusion layer to obtain the gas diffusion layer with anti-reflection capability.
Optionally, the graphene oxide, the solvent and the Ni 3 S 2 The mass ratio of the solid is 1-5:2-3:2-10.
Optionally, the mass ratio of the dispersing agent to the cross-linking agent is 1-5:1-5.
Optionally, the Ni 3 S 2 The preparation method of the solid comprises the following steps:
respectively obtaining thiourea and foam nickel;
adding the thiourea and the foam nickel into a solvent for mixing, and then adding N, N-dimethylformamide for mixing to obtain a suspension;
preserving the temperature of the suspension at a preset temperature, and naturally cooling and filtering to obtain Ni 3 S 2 A solid.
Optionally, the mass ratio of the thiourea, the foam nickel, the solvent and the N, N-dimethylformamide is 1-5:2-10:2-10:5-20.
Optionally, the preset temperature is 130-150 ℃, and the heat preservation time is 4-6 h.
Optionally, the preparation method of the graphene oxide comprises the following steps:
respectively obtaining concentrated sulfuric acid, concentrated nitric acid, graphite, potassium permanganate, hydrogen peroxide and hydrochloric acid;
mixing the concentrated sulfuric acid, the concentrated nitric acid and the graphite, and then adding the potassium permanganate for heating to obtain a first mixed solution;
and adding a solvent, the hydrogen peroxide and the hydrochloric acid into the first mixed solution for sedimentation, and taking out the lower-layer solid to obtain graphene oxide.
Optionally, the mass-volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the graphite is 10 mL-15 mL:15 mL-25 mL:5g.
Optionally, the heating temperature is 40-50 ℃, and the heating time is 0.5-1.5 h.
The dispersing agent comprises at least one of isopropanol, ethanol, N-dimethylformamide, ethylene glycol and propanol;
the cross-linking agent comprises at least one of phenolic resin, dopamine, aziridine and polyvinyl alcohol, wherein the dispersing agent can be isopropanol, ethanol, N-dimethylformamide, ethylene glycol or propanol, and the cross-linking agent can be phenolic resin, dopamine, aziridine and polyvinyl alcohol.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the preparation method of the microporous layer slurry with anti-reverse polarity capability provided by the embodiment of the application comprises the steps of adding a catalyst Ni capable of improving hydrolysis reaction activity 3 S 2 The catalyst-supported graphene oxide is loaded on graphene oxide, and the graphene oxide loaded with the catalyst is uniformly distributed through the use of the dispersing agent and the cross-linking agent, so that microporous layer slurry with anti-counter electrode capability is obtained, and the microporous layer slurry is sprayed on a commercial gas diffusion layer, so that the catalyst is largely loaded on the gas diffusion layer, the water electrolysis reaction activity can be rapidly improved, the opportunity of water and carbon reaction is reduced, and the counter electrode nature is caused by the mutual competition between two chemical reactions, namely the reaction of water and carbon and the competition between the electrolysis reactions of water, so that the anti-counter electrode capability of the gas diffusion layer can be effectively improved through the influence of the catalyst on the two chemical reactions, and the anti-counter electrode capability of the fuel cell is further improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method according to an embodiment of the present disclosure;
FIG. 2 is a diagram of Ni provided in an embodiment of the present application 3 S 2 A flow diagram of a method for preparing a solid;
fig. 3 is a schematic flow chart of a preparation method of graphene oxide according to an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the embodiments of the present application, are within the scope of the present application.
The inventive thinking of the invention is: when the automobile is continuously started and stopped or when fuel shortage happens suddenly, the gas distribution in the battery is uneven, which leads to insufficient gas supply of the battery body, sharp attenuation of the voltage of the single battery is caused, and the voltage of the single battery is even changed into negative voltage, so that the reverse polarity occurs. The counter electrode will reduce the performance of the cell, the hydrogen and oxygen in the reaction chamber are mixed with each other, and even there is a risk of explosion, so the fuel cell must have the capability of resisting the counter electrode.
In one embodiment of the present application, as shown in fig. 1, a method for preparing a gas diffusion layer with anti-inversion capability is provided, where the method includes:
s1, respectively obtaining graphene oxide and Ni 3 S 2 Solids, dispersants, and crosslinkers;
s2, adding the graphene oxide into a solvent for mixing, and then adding the Ni 3 S 2 Mixing the solids to obtain a water electrolysis catalyst;
s3, mixing the water electrolysis catalyst, the dispersing agent and the cross-linking agent, and dispersing to obtain microporous layer slurry with anti-counter electrode capability;
s4, spraying the microporous layer slurry on a commercial gas diffusion layer to obtain a gas diffusion layer with anti-counter electrode capability;
wherein the solvent may be deionized water.
In some alternative embodiments, the graphene oxide, the solvent, and the Ni 3 S 2 The mass ratio of the solid is 1-5:2-3:2-10.
In the embodiment of the application, graphene oxide, solvent and Ni 3 S 2 The positive effects of the mass ratio of the solid being 1-5:2-3:2-10 are that the graphene oxide can ensure that the Ni is oxidized by the graphene within the mass ratio range 3 S 2 The solid is fully loaded, and the solvent plays a role of a dispersing agent, thereby promoting Ni 3 S 2 Dispersion of solids, thereby ensuring Ni 3 S 2 The solid is uniformly loaded on the graphene oxide, so that uniform distribution of anti-counter electrode capability of the microporous layer slurry is ensured; when the ratio of the mass values is larger or smaller than the end value of the range, the graphene oxide cannot convert Ni 3 S 2 The solids are sufficiently loaded so that the distribution of the anti-counter electrode capability of the microporous layer slurry cannot be ensured, and the performance of the fuel cell is also reduced.
In some alternative embodiments, the mass ratio of the dispersant to the crosslinker is 1-5:1-5.
In the embodiment of the application, the positive effect that the mass ratio of the dispersing agent to the cross-linking agent is 1-5:1-5 is that the graphene oxide and the Ni can be ensured within the mass ratio range 3 S 2 The solid is uniformly dispersed in the solvent by the dispersing agent, and Ni can be ensured at the same time 3 S 2 The solid is loaded on the graphene oxide through a cross-linking agent, so that the preparation of microporous layer slurry with anti-counter electrode capability is completed, and the anti-counter electrode capability of the gas diffusion layer is further ensured; when the value of the mass ratio is larger or smaller than the end value of the range, the waste of raw materials is caused, and Ni cannot be ensured 3 S 2 The solid can be completely loaded by the graphene oxide, and the final gas diffusion layer is affectedAnti-counter pole capability.
In some alternative embodiments, as shown in FIG. 2, the Ni 3 S 2 The preparation method of the solid comprises the following steps:
s101, respectively obtaining thiourea and foam nickel;
s102, adding the thiourea and the foam nickel into a solvent for mixing, and then adding N, N-dimethylformamide for mixing to obtain a suspension;
s103, preserving the temperature of the suspension at a preset temperature, and naturally cooling and filtering to obtain Ni 3 S 2 A solid.
In the examples of the present application, nickel foam is used as Ni 3 S 2 One of the solid raw materials can be effectively reacted with thiourea and N, N-dimethylformamide by utilizing the characteristics of foam nickel, thereby obtaining Ni with excellent water electrolysis catalysis performance 3 S 2 A solid catalyst.
In some alternative embodiments, the mass ratio of the thiourea, the nickel foam, the solvent, and the N, N-dimethylformamide is 1-5:2-10:2-10:5-20.
In the embodiment of the application, the mass ratio of thiourea, foam nickel, solvent and N, N-dimethylformamide is 1-5:2-10:2-10:5-20, and the positive effects are that Ni can be ensured within the mass ratio range 3 S 2 The generation of solid is sufficient, thereby ensuring the reaction between the raw materials to be sufficient and forming sufficient Ni 3 S 2 A solid; when the mass ratio is larger or smaller than the end value of the range, the partial raw materials are excessive, the reaction between the raw materials can not be ensured to be complete, and enough Ni can not be obtained 3 S 2 The solid can effectively improve the water electrolysis reaction activity, thereby influencing the anti-counter electrode capability of the gas diffusion layer.
In some alternative embodiments, the preset temperature is 130 ℃ to 150 ℃, and the time of heat preservation is 4 hours to 6 hours, wherein the preset temperature can be 130 ℃, 140 ℃ and 150 ℃, and the time of heat preservation can be 4 hours, 5 hours and 6 hours.
In the embodiment of the application, the preset temperature is 130-150 ℃, and the positive effects are that in the temperature range, thiourea, foam nickel and N, N-dimethylformamide can be ensured to fully react, so that sufficient Ni is obtained 3 S 2 A solid; when the temperature is higher or lower than the end of the range, the reaction proceeds insufficiently, resulting in Ni 3 S 2 The insufficient amount of solid produced affects the effective improvement of the water electrolysis reaction activity, thereby affecting the anti-polarity capability of the gas diffusion layer.
The heat preservation time is 4-6 h, and the positive effect is that in the time range, the thiourea, the foam nickel and the N, N-dimethylformamide can be ensured to fully react, thereby obtaining sufficient Ni 3 S 2 The solid, when the time is greater than or less than the end value of the range, will result in too long reaction time, affecting the overall time-consuming process, or too short reaction time, affecting the full progress of the reaction.
In some alternative embodiments, the method for preparing graphene oxide includes:
s201, respectively obtaining concentrated sulfuric acid, concentrated nitric acid, graphite, potassium permanganate, hydrogen peroxide and hydrochloric acid;
s202, mixing the concentrated sulfuric acid, the concentrated nitric acid and the graphite, and then adding the potassium permanganate for heating to obtain a first mixed solution;
s203, adding a solvent, the hydrogen peroxide and the hydrochloric acid into the first mixed solution for sedimentation, and taking out the lower layer of solid to obtain graphene oxide; wherein the solvent may be deionized water.
In the embodiment of the application, the graphite is treated by adopting a plurality of groups of oxides and based on a Hummers method, and then the graphene is further oxidized and separated by hydrogen peroxide and hydrochloric acid, so that the obtained graphene oxide is fully oxidized, and meanwhile, the added hydrogen peroxide and hydrochloric acid can change the solubility of a solvent, so that the sedimentation of the graphene oxide is ensured, and the graphene oxide is conveniently obtained.
In some alternative embodiments, the mass to volume ratio of the concentrated sulfuric acid, the concentrated nitric acid, and the graphite is 10 mL-15 mL:15 mL-25 mL:5g.
In the embodiment of the application, the mass-volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the graphite is 10 mL-15 mL:15 mL-25 mL:5g, and the positive effects are that in the mass-volume ratio range, the graphite can be ensured to be subjected to preliminary oxidation by a Hummers method, the structure of the graphite is approximately formed, the graphene oxide can be fully formed in the subsequent oxidation stage, the content of sulfate ions is ensured to be stable, and the sulfate radical can be replaced completely after the subsequent hydrochloric acid treatment, so that pure graphene oxide is obtained.
In some alternative embodiments, the heating temperature is 40 ℃ to 50 ℃ and the heating time is 0.5h to 1.5h, wherein the heating temperature can be 40 ℃, 45 ℃ and 50 ℃, and the heating time can be 0.5h, 1h and 1.5h.
In the embodiment of the application, the heating temperature is 40-50 ℃, and the positive effects are that in the temperature range, the graphite can be fully oxidized by the concentrated sulfuric acid, the concentrated nitric acid and the potassium permanganate, and the normal operation of the reaction is ensured; when the temperature is higher or lower than the end value of the range, the oxidation degree of graphite is insufficient, and the generation of graphene oxide is affected.
In some alternative embodiments, the dispersant comprises at least one of isopropyl alcohol, ethanol, N-dimethylformamide, ethylene glycol, propanol;
the cross-linking agent comprises at least one of phenolic resin, dopamine, aziridine and polyvinyl alcohol.
In the embodiment of the application, the positive effects of the dispersant including at least one of isopropanol, ethanol, N-dimethylformamide, ethylene glycol and propanol are that the graphene oxide and Ni can be ensured within the limited dispersant range 3 S 2 The solid is fully dispersed in the solvent, so that the uniformity of the anti-polar capability in the microporous layer slurry is ensured.
The cross-linking agent comprises at least one of phenolic resin, dopamine, aziridine and polyvinyl alcohol, has the positive effects that Ni can be ensured within the limited cross-linking agent range 3 S 2 The solid is loaded by graphene oxide, so that the anti-counter electrode capability of the microporous layer slurry is ensured.
Example 1
As shown in fig. 1, a method for preparing a gas diffusion layer with anti-reverse-polarity capability includes:
s1, respectively obtaining graphene oxide and Ni 3 S 2 Solids, dispersants, and crosslinkers;
s2, adding graphene oxide into a solvent for mixing, and then adding Ni 3 S 2 Mixing the solids to obtain a water electrolysis catalyst;
s3, mixing a water electrolysis catalyst, a dispersing agent and a cross-linking agent, and dispersing to obtain microporous layer slurry with anti-counter electrode capability;
s4, spraying the microporous layer slurry on commercial carbon paper SGL-22bb to obtain a gas diffusion layer with anti-counter electrode capability;
wherein the solvent is deionized water, ultrasonic dispersion is adopted for dispersion, the power of ultrasonic dispersion is 600W, and the time of ultrasonic dispersion is 60min.
Graphene oxide, solvent and Ni 3 S 2 The mass ratio of the solids is 1g to 2g.
The mass ratio of the dispersant to the crosslinking agent is 1 g/1 g.
As shown in FIG. 2, ni 3 S 2 The preparation method of the solid comprises the following steps:
s101, respectively obtaining thiourea and foam nickel;
s102, adding thiourea and foam nickel into a solvent for mixing, and then adding N, N-dimethylformamide for mixing to obtain a suspension;
s103, preserving the temperature of the suspension at a preset temperature, and naturally cooling and filtering to obtain Ni 3 S 2 A solid.
The mass ratio of thiourea, foam nickel, solvent and N, N-dimethylformamide is 1g to 2g to 5g.
The preset temperature is 140 ℃, and the heat preservation time is 6 hours.
As shown in fig. 3, the preparation method of graphene oxide includes:
s201, respectively obtaining concentrated sulfuric acid, concentrated nitric acid, graphite, potassium permanganate, hydrogen peroxide and hydrochloric acid;
s202, mixing concentrated sulfuric acid, concentrated nitric acid and graphite, and then adding potassium permanganate for heating to obtain a first mixed solution;
s203, adding 15mL of a solvent, 20mL of hydrogen peroxide and 20mL of hydrochloric acid into the first mixed solution for sedimentation, and taking out the lower layer of solid to obtain graphene oxide; wherein the solvent is deionized water.
The mass-volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the graphite is 10mL to 15mL to 5g.
The heating temperature was 40℃for 1h.
The dispersing agent is isopropanol;
the cross-linking agent is dopamine.
Example 2
Example 2 and example 1 were compared, and the difference between example 2 and example 1 is that:
graphene oxide, solvent and Ni 3 S 2 The mass ratio of the solids is 2g to 4g.
The mass ratio of the dispersant and the crosslinking agent is 2g to 2g.
The mass ratio of thiourea, foam nickel, solvent and N, N-dimethylformamide is 2g to 5g to 10g.
The preset temperature is 140 ℃, and the heat preservation time is 6 hours.
The mass-volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the graphite is 10mL to 15mL to 5g.
The heating temperature was 40℃and the heating time was 1h.
The dispersing agent is isopropanol;
the cross-linking agent is dopamine.
Example 3
Example 3 was compared with example 1, and the difference between example 3 and example 1 was:
graphene oxide, solvent and Ni 3 S 2 The mass ratio of the solids is 2g to 3g to 4g.
The mass ratio of the dispersant to the crosslinking agent is 3g:3g.
The mass ratio of thiourea, foam nickel, solvent and N, N-dimethylformamide is 4g to 8g to 10g.
The preset temperature is 140 ℃, and the heat preservation time is 6 hours.
The mass-volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the graphite is 12mL to 20mL to 5g.
The heating temperature was 40℃and the heating time was 1h.
The dispersing agent is isopropanol;
the cross-linking agent is dopamine.
Example 4
Example 4 and example 1 were compared, and example 4 and example 1 differ in that:
graphene oxide, solvent and Ni 3 S 2 The mass ratio of the solids is 5g to 3g to 10g.
The mass ratio of the dispersant to the cross-linking agent is 5g to 5g.
The mass ratio of thiourea, foam nickel, solvent and N, N-dimethylformamide is 5g to 10g to 20g.
The preset temperature is 140 ℃, and the heat preservation time is 6 hours.
The mass-volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the graphite is 15mL to 25mL to 5g.
The heating temperature was 40℃and the heating time was 1h.
The dispersing agent is isopropanol;
the cross-linking agent is dopamine.
Comparative example 1
Comparative example 1 and example 1 are compared, and the difference between comparative example 1 and example 1 is that:
the gas diffusion layer is commercial SGL-22bb carbon paper.
Related experiments:
the gas diffusion layers obtained in examples 1 to 4 and comparative example 1 were collected, respectively, and performance was measured, and the results are shown in Table 1.
Test method of related experiment:
conductivity value: the gas diffusion layers are matched with catalytic layers of the same specification, and are configured on a single cell test bench for conductivity measurement, and the model of the test bench is SCRIBNER 850e.
Contact angle: the GDL surface was tested using a DSA100S contact angle tester in 5 μl drops, with each sample being averaged 5 times.
Anti-counter time: the detection is carried out by using T/CAAMTB 12-2020 proton exchange membrane fuel cell membrane electrode test method.
TABLE 1
Specific analysis of table 1:
the conductivity value refers to the conductivity degree of the prepared gas diffusion layer, and the higher the conductivity value is, the better the conductivity of the gas diffusion layer is.
The contact angle refers to the degree of hydrophilicity of the gas diffusion layer produced, and the smaller the contact angle, the more hydrophilic the gas diffusion layer.
The anti-counter-electrode time refers to continuous counter-electrode running time from the occurrence of the counter-electrode phenomenon of the fuel cell to the decay of the current density to within 10%, and the longer the anti-counter-electrode time is, the stronger the anti-counter-electrode capability of the dye cell is.
From the data of examples 1-4,
if graphene oxide and Ni are adopted in the application 3 S 2 The microporous layer slurry formed by the solid can effectively improve the conductivity of the gas diffusion layer, and meanwhile, the contact angle is reduced due to the hydrophilic graphene oxide, but the whole contact angle is still more than 120 degrees, and the microporous layer slurry still belongs to a super-hydrophobic material, so that the drainage property of the gas diffusion layer is not greatly influenced.
In sprayingGraphene oxide supported Ni 3 S 2 After the solid, the anti-reverse polarity performance of the gas diffusion layer is obviously enhanced; this demonstrates that the introduction of the catalyst for the hydrolysis reaction significantly activates the reaction of the electrolyzed water, thereby reducing the decomposition of carbon during the fuel cell reaction, and thus allowing an increase in the time to counter-electrode.
From the data of comparative example 1, it can be seen that:
if the untreated carbon paper is used as the diffusion layer, although the contact angle is larger, the conductivity value and the anti-counter-electrode time are lower, and the method of the application is described from the reverse side, so that the conductivity value of the gas diffusion layer can be effectively improved, and the anti-counter-electrode time can be effectively prolonged.
To verify graphene oxide loaded Ni 3 S 2 The solid is used as the influence degree of the catalyst on the membrane electrode, and the application also carries out membrane electrode experiments:
the gas diffusion layers obtained in examples 1 to 4 and comparative example 1 were assembled into membrane electrodes under the same conditions and on the same substances, and the open circuit voltages of the membrane electrodes were measured, respectively, and the results are shown in table 2.
TABLE 2
Specific analysis of table 2:
as is clear from Table 2, when the membrane electrode was assembled from the prepared gas diffusion layers, the cell performance was tested, and the open circuit voltage was substantially the same, indicating that the graphene oxide was loaded with Ni 3 S 2 The solid is introduced into the microporous layer slurry of the gas diffusion layer as a catalyst, and the activity of the Pt/C catalyst is not reduced, so that the problem of reduced catalyst activity can be avoided.
One or more technical solutions in the embodiments of the present application at least further have the following technical effects or advantages:
(1) The method provided by the embodiment of the application comprises the steps of introducing a catalyst Ni capable of improving the activity of hydrolysis reaction into microporous layer slurry 3 S 2 At the same time Ni 3 S 2 The solid is loaded on the graphene oxide, so that a large amount of catalyst is loaded on the gas diffusion layer, the water electrolysis reaction activity can be rapidly improved, the opportunity of water and carbon reaction is reduced, and the anti-counter electrode capability of the gas diffusion layer is improved.
(2) According to the method provided by the embodiment of the application, the introduced graphene oxide can serve as a catalyst Ni 3 S 2 The solid carrier can also remarkably reduce the contact resistance between the gas diffusion layer and the catalytic layer, thereby improving the power generation efficiency of the fuel cell.
(3) The method provided in the embodiment of the application, although Ni is added in the gas diffusion layer 3 S 2 The solid-supported graphene oxide has no great influence on the drainage performance of the gas diffusion layer and the catalytic activity of the Pt/C catalyst.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. A method of making a gas diffusion layer resistant to counter-polar, the method comprising:
respectively obtain graphene oxide and Ni 3 S 2 Solids, dispersants, and crosslinkers;
adding the graphene oxide into a solvent for mixing, and then adding the Ni 3 S 2 Mixing the solids to obtain a water electrolysis catalyst;
mixing the water electrolysis catalyst, the dispersing agent and the cross-linking agent, and dispersing to obtain microporous layer slurry with anti-counter electrode capability;
spraying the microporous layer slurry on a commercial gas diffusion layer to obtain a gas diffusion layer with anti-reflection capability;
the graphene oxide, the solvent and the Ni 3 S 2 The mass ratio of the solids is 1-5:2-3:2-10;
the mass ratio of the dispersing agent to the cross-linking agent is 1-5:1-5; the dispersing agent is isopropanol, and the crosslinking agent is dopamine;
the Ni is 3 S 2 The preparation method of the solid comprises the following steps:
respectively obtaining thiourea and foam nickel;
adding the thiourea and the foam nickel into a solvent for mixing, and then adding N, N-dimethylformamide for mixing to obtain a suspension;
preserving the temperature of the suspension at a preset temperature, and naturally cooling and filtering to obtain Ni 3 S 2 A solid;
the mass ratio of the thiourea to the foam nickel to the solvent to the N, N-dimethylformamide is 1-5:2-10:2-10:5-20.
2. The method according to claim 1, wherein the preset temperature is 130 ℃ to 150 ℃ and the time for heat preservation is 4 hours to 6 hours.
3. The method according to claim 1, wherein the preparation method of graphene oxide comprises:
respectively obtaining concentrated sulfuric acid, concentrated nitric acid, graphite, potassium permanganate, hydrogen peroxide and hydrochloric acid;
mixing the concentrated sulfuric acid, the concentrated nitric acid and the graphite, and then adding the potassium permanganate for heating to obtain a first mixed solution;
and adding a solvent, the hydrogen peroxide and the hydrochloric acid into the first mixed solution for sedimentation, and taking out the lower-layer solid to obtain graphene oxide.
4. A method according to claim 3, wherein the mass to volume ratio of the concentrated sulfuric acid, the concentrated nitric acid and the graphite is 10mL to 15mL to 25mL to 5g.
5. A method according to claim 3, wherein the heating is at a temperature of 40 ℃ to 50 ℃ for a time of 0.5h to 1.5h.
6. The method of claim 1, wherein the dispersant comprises at least one of isopropanol, ethanol, N-dimethylformamide, ethylene glycol, propanol;
the cross-linking agent comprises at least one of phenolic resin, dopamine, aziridine and polyvinyl alcohol.
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